Coated articles



United States Patent Filed Jan. 25, 1961, Ser. No. 84,751

This invention concerns coated floors, walls, or floor or wall coverings, and it is particularly concerned with the preperation of flexible, tough, stain-resistant, abrasionresistant, water-resistant, and alkali-resistant coatings on flooring materials. This application is a continuation-inpart of our copending application Serial No. 17,475, filed March 25, 1960, now abandoned.

A primary object of the present invention is to provide wear-resistant coatings of synthetic polymer latices on various substrates and especially those which are capable of serving as floors, walls, wall-coverings, or floorcoverings, particularly of the cloth (e.g., Sanitas), feltbase, and linoleum type. Another object of the present invention is to provide for coating such substrates with aqueous dispersions of synthetic copolymers which are adapted to be applied at room temperature and are capable of producing wear-resistant coatings which are sufliciently flexible and tough to permit the coated substrates to be flexed so that they can be rolled upon themselves. Other objects and advantages will be apparent from the description hereinafter.

Felt-base is normally prepared by printing a decorative wearing surface upon a suitably treated carrier backing. Generally speaking, the backing is formed of an asphalt-saturated felt carrying one or more seal-coats which serve to render the surface of the backing sufl'iciently smooth to receive the comparatively thin film of paint which forms the decorative wearing surface of the floor covering. While felt-base material is less expensive then most other floor-covering of its type, its wearing qualities are poor due to relatively small thickness of the decorative wearing surface. It is the purpose of our invention to up-grade the wearing qualities of such a floor covering by providing a clear, tough, stain-resistant wear layer over the decorative surface.

Linoleum is manufactured by depositing a mixture of filler, pigment, and linoleum binder, generally obtained by oxidizing a drying oil in the presence of a resin, upon a suitable carrier backing, for example, saturated felt. The mass is then stored or cured for a considerable period of time to obtain the desired properties of resilience and flexibility in the wearing surface. Linoleum is a comparatively expensive flooring material because of the raw materials from which it is manufactured and further because of the techniques employed. Its wearing properties are considerably better than are attainable with the above-described felt base. With the use of applicants invention, its general appearance as well as wearing properties are considerably improved.

In accordance with the present invention, it has been found that outstanding coating compositions adapted to produce clear or pigmented, tough, flexible, stain-resistant, and wear-resistant coatings on various substrates, including asphalt tile, woven cloth, felt base, and linoleum, can be produced by applying as the topcoat an aqueous latex containing a water-insoluble emulsion copolymer of a mixture of 35 to 65% by weight of vinylidene chloride with 65 to 35% by weight of a monomeric material selected from the group consisting of (a) methyl acrylate, (b) n-propyl methacrylate, (c) butyl methacrylate, and (d) mixtures of (1) at least one member having a hardening effect selected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with 3,130,176 Patented Apr. 21, 1964 an alkanol having 1 to 3 carbon atoms such as methyl, ethyl, n-propyl, and isopropyl methacrylate, with (2) at least one member having a softening effect selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms, the amount of (1) being from 10 to 50% by weight of the total monomer mixture (including vinylidene chloride) and the amount of (2) being from 15 to 55% by weight of the total monomer mixture (including vinylidene chloride), with the proviso that at least 35 by Weight of the copolymer is formed of at least one of the aforesaid esters mentioned in (1) or (2).

Instead of the copolymer as just defined, there may be used a blend of two or more ditferent copolymers of such composition that the average composition of the blend will meet the compositional definitions given hereinabove for a straight or simple copolymer. Thus, the average composition of the blend must comprise 35 to 65% by Weight of vinylidene chloride. For example, various copolymers of methyl acrylate, n-propyl methacrylate, or butyl methacrylate containing from 3565% by weight of vinylidene chloride may be blended at will. Again, copolymers of 3565% vinylidene chloride with at least one hardening monomer and at least one softening monomer (as defined in part (d) of the definition of the copolymers already given hereinabove) may be blended with each other to provide an average copolymer composition within the scope of the definition of part (d) hereinabove. One or more of the latter type of copolymers may also be blended with one or more of the aforesaid 3565% vinylidene chloride copolymers of methyl acrylate, n-propyl methacrylate, and butyl methacrylate. Particularly valuable blends are obtained by mixing (A) at least one copolymer of 35 to 65% by weight of vinylidene chloride and 35-65% by Weight of a hardening comonomer of part (d) (1) hereinabove and 0 to 20% by weight of a softening monomer of part (d) (2) hereinabove with (B) at least one copolymer of 35 to 65% of vinylidene chloride, 10 to 30% of at least one hardening monomer (d) (l), and 20 to 55% of at least one softening monomer of part (d) (2). The use of blends has the advantage of producing an improved combination of toughness, hardness, and block-resistance.

A small proportion from about 0.25% to 5% of the copolymer (or of one or more or all of the copolymers when a blend is used) may be formed of monomers imparting hydrophilic characteristics to the polymer such as acrylic acid, methacrylic acid, itaconic acid, ,B-hydroethyl acrylate, fi-hydroxyethyl vinyl ether, allyl glycidyl ether, and the like. \Vhen the hydrophilic monomer is of hardening character, such as the acids mentioned, it may replace a corresponding amount of the hardening comonomer (1) in the copolymers from mixture (d) above whereas hydrophilic monomers of softening character may partially replace the softening comonomer (2).

it is essential that the copolymer (and each copolymer therein when a blend is used) contain at least 35% by weight of vinylidene chloride in order to avoid staining and to impart superior toughness characteristics to the polymer systems. Preferred results are, however, obtained with at least 40% by weight of vinylidene chloride. The maximum amount of vinylidene chloride in the copolymer (or copolymers) should not exceed 65% by weight and it is preferred that the maximum be 60% or less. If less than 35 by weight of the copolymer (or copolymers) is composed of one or more of the esters mentioned, the films acquire a yellowish color and they are insufficiently resistant to ultraviolet light for practical purposes.

The several components of the copolymers cooperate in providing a stain-resistant, hard, and yet flexible film which has outstanding ability to avoid the picking up of dirt which is particularly important in both wall and floor finishes. In the ternary copolymers, the use of an excessive amount of the softening monomer over the limit specified causes a loss of the resistance to the picking up of dirt and hardness as well. In these ternary copolymers, the hardening and softening comonomers serve to produce a hard, wear-resistant coating which nevertheless is still adequately flexible for the purposes at hand, which in some cases, as in the case of felt base or linoleum floor coverings, may involve rolling of the coated product upon itself.

In general, the preparation of the copolymer latex is obtained by conventional emulsion polymerization techniques using any conventional free-radical initiator and any suitable emulsifier, either of anionic, non-ionic, or cationic character.

As initiators any free-radical initiator may be used, of which the peroxygen compounds are representative. Organic peroxides and hydroperoxides as well as hydrogen peroxide and inorganic persulfates are useful. Examples include acetyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, phenylcyclohexane hydroperoxide, and ammonium or potassium persulfate.

Various activators may be employed such as ascorbic acid, isoascorbic acid, sodium-formaldehyde sulfoxylate, alkali metal hydrosulfites, and metabisulfites.

The proportion of activator may be comparable to that of the initiator such as from about 0.1% to 1% by weight of the total of the polymer and monomer weights. Besides employing activators, promoters such as traces of copper, silver, or iron ions may be employed.

Best results are obtained when the amount of excess surface-active agent over that required to confer adequate stability to the latex is kept at a minimum and when shortstops, anti-oxidants, metal salts, and other additives are not of such a nature or present in sufiiciently large quantities so as to impart undesirable properties to the copolymers and films made therefrom.

Thickening agents and sequestering agents may be employed. Examples of thickening agents include polyvinyl alcohol, sodium polyacrylate, sodium salts of copolymers of methacrylic acid and methyl methacrylate, sodium alginate, carboxymethyl cellulose, methyl cellulose, casein, and hydroxyethyl cellulose. Examples of sequestering agents include sodium citrate, sodium pyrophosphate, and Versene (the sodium salt of ethylene diamine tetraacetic acid).

The aqueous dispersion of the copolymer or blend may be applied at a concentration from about 1 to 65% or more. Preferably, however, it is diluted to a concentration of about 40 to 55% by weight of copolymer on the weight of the entire dispersion. Such dilution, of course, is preferably accomplished by the addition of water. During the coating operation, the composition may be applied at a temperature from room temperature up to 100 0., depending upon the minimum film-forming temperature of the dispersion. In some cases the character of the substrate or' prevalent manufacturing conditions do not allow the use of elevated temperatures for fluxing and drying of the coatings. In such event it may be desirable to incorporate into the dispersion a plasticizer which could be of either permanent nature, i.e., remaining in the film after coalescence, or of the fugitive type, commonly called a fluxing-aid or a coalescing-aid, which would leave the film once film continuity has been achieved. The latter type may be preferred since, due to the relatively high volatility of the modifiers, the final film hardness of the copolymer would not be lowered. The amount of plasticizer of either type may be as high as 70% by weight of the copolymer weight, with the exact quantity depending on the minimum film-formation temperature of the unplasticized copolymer and the ambient temperature available for film deposition.

The so-called permanent plasticizers may include various high-boiling esters of phthalic acid such as dimethyl phthalate, dibutyl phthalate, butylbenzyl phthalate, etc., esters of sebacic acid such as dioctyl sebacate and many other substances which will function as plasticizers for the particles in the dispersion to facilitate their deformation during the process of film formation leading to the attainment of film continuity.

The fugitive plasticizers, usually called fluxing or coalescing aids, normally consist of solvents or relatively low-boiling plasticizers for the copolymer or copolymers. The boiling points of these compositions at (760 mm. Hg) fall within a range of to 250 C. and preferably in the range of to 215 C. Examples of the fiuxing aids (and their boiling points) are 2-ethoxyethyl acetate (156 C.), 2-butoxyethyl acetate (191 C.), diethyleneglycol monoethylether (201.9 C.), diethyleneglycol (mono)-methylether (193 C.), 2-(2-butoxyethoxy)ethyl acetate (246 C.), isophorone (215 C.), and benzyl alcohol (205 C.).

The coating compositions of the present invention may be applied to all sorts of substrates and are especially valuable for the coating of floor coverings and wall coverings of felt-base and linoleum types. Besides the latter, the compositions may be applied to linoleum, wood, asphalt tile, rubber tile, vinyl resin tile, leather, and metal surfaces. They are useful also as the topcoating layers over any of these substrates on which pigmented basecoats have been applied and which it is desired to protect against abrasion and scuffing. For example, on wooden fioors, they may be employed as a substitute for varnish or as the top wear-layer over one or more preliminary coats of varnish. In the case of linoleum, felt-base coverings, and the various plastic tile compositions mentioned above, pigmented coatings may be applied prior to the vinylidene chloride copolymer or the copolymer may be applied directly to the composition of the tile, in which event it may be desirable to include a pigment or dye. Of course, in any case, a single coat of the copolymer dispersion or a series of such coats may be applied and one or more of such coats may be pigmented if desired. The thickness of the coating may vary from about /2 mil to- 20 mils or more.

An important feature of the present invention is the employment of emulsion copolymers which are of characteristic highmolecular weight, generally from about 500,000 to several million, e.g., ten million, viscosity average. Not only is the high molecular weight important in contributing to the toughness and wear-resistance of the coatings, but also the use of aqueous dispersions in the coating operation makes it possible to attain the toughness and other properties associated with high molecular weight without the introduction of excessively high viscosity in the coating composition. The use of aqueous dispersions is also quite advantageous from the standpoint of expense. It is unnecessary to take special precautions against fire and toxicity, which the use of solutions in organic solvents frequently entail.

In the following examples which are illustrative of the invention, the parts and. percentages are by weight unless otherwise indicated.

Example 1 Percent Ethyl acrylate 40 Methyl methacrylate 20 Vinylidene chlor 40 The final total solids concentration of the emulsion is adjusted to 8.0, using 43.5%. The pH of the emulsion is 14% aqueous NH OH.

(b) A mixture of 4.4 parts by weight of butoxyethyl acetate, 4.4 parts by Weight of water, and .01 part by Weight of t-octylphenoxypolyethoxyethanol containing about oxyethylene units is prepared and introduced into 100 parts by weight of the neutralized emulsion polymer obtained in part (a), and the resulting mixture is then modified by the addition of 3.6 parts by weight of an NH OH solution of commercial grade of casein prepared at 12.5% total solids.

(c) The composition obtained in part (b) is then applied as a top-coating to a section of felt-base material consisting of an asphalt-saturated felt-base carrying a decorative design superimposed on three pigmented base coats. The coated assembly is then dried in a circulating oven at 80 C. for a period of two hours. The amount of dispersion used produces a dried film thickness of .803 inch. The surface with the coating upon it is characterized by a high degree of gloss and excellent resistance to marring, and the finished floor covering could be rolled upon itself without showing any signs of crazing. The clear wear layer thus deposited is completely resistant to staining by tincture of iodine, tincture of merthiolate, lipstick, and animal and vegetable fats. It shows no whitening upon prolonged exposure to water or mild alkali (3% NH OH). Actual floor tests under foot-traffic conditions show the coating to have a superior resistance to wear, marring, dirt pick-up, and scufiing in comparison to commercial felt-base asphalt and linoleum fioor coverings.

Example 2 Percent Methyl acrylate 60 Vinylidene chlorid 40 The final total solids concentration of the emulsion is 48%. The pH of the emulsion was adjusted to 8.0, using 14% aqueous NHgOH.

(b) A mixture of 4.8 parts by weight of butoxyethyl acetate, 4.8 parts by weight of water, and .01 part by Weight of t-octylphenoxypolyethoxyethanol containing about 10 oxyethylene units is prepared and introduced into 100 parts by weight of the neutralized emulsion polymer obtained in part (a), and the resulting mixture is then modified by the addition of 3.8 parts by weight of an NH OH solution of commercial grade of casein prepared at 12.5 total solids.

(c) The composition obtained in part (b) is applied to a felt-base floor-covering as in Example 1(a) with similar results.

Example 3 The procedure of Example 2 is repeated with a copolymer prepared in similar fashion from a mixture of:

Percent 2-ethylhexyl acryl 25 Methyl methacryl 35 Vinylidene chlor 40 Example 4 The procedure of Example 2 is repeated with a copolymer prepared in similar fashion from a mixture of:

Percent Methyl acryl 35 Vinylidene chlori 65 The composition is applied both to felt-base wall-covering and flooring material, linoleum, vinyl tile, and asphalt tile.

6 The coating obtained is a clear, stain-resistant wear layer comparable to that obtained in Example 1.

Example 5 The procedure of Example 1 is repeated except that only 3% (on monomer weight) of the emulsifier is employed and the mixture of monomers consists of:

Percent Ethyl acrylate 45 Styrene 20 Vinylidene chloride 35 Coatings of the resulting composition applied to felt-base and linoleum are clear, are resistant to staining, and have excellent Wear characteristics.

Example 6 The procedure of Example 1 is repeated except that only 3% (on monomer weight) of the emulsifier is employed and the mixture of monomers consists of:

Percent Butyl methacryla 50 Methyl methacrylate l0 Vinylidene chloride 40 Instead of casein, 3 parts by Weight of sodium alginate is added. Coatings of the resulting composition applied to felt-base and linoleum are clear, are resistant to staining, and have excellent wear characteristics.

Example 7 The procedure of Example 1 is repeated except that only 3% (on monomer weight) of the emulsifier is employed and the mixture of monomers consists of:

Percent Ethyl acrylate 5O Methyl methacrylate 7 Methacrylic acid 3 Vinylidene chloride 40 The procedure of Example 1 is repeated except that only 3% (on monomer weight) of the emulsifier is employed and the mixture of monomers consists of:

Percent Butyl acrylate 40 Vinyltoluene 25 Vinylidene chloride 35 Coatings of the resulting composition applied to felt-base and linoleum are clear, are resistant to staining, and have excellent wear characteristics.

Example 9 The procedure of Example 2 is repeated with a copolymer prepared in similar fashion from a mixture of:

Percent nPropyl methacrylate 60 Vinylidene chloride 40 The composition is applied both to felt-base wall-covering and flooring material, linoleum, vinyl tile, and asphalt tile. The coating obtained is a clear, stain-resistant Wear layer comparable to that obtained in Example 1.

Example 10 The procedure of Example 2 is repeated with a copolymer prepared in similar fashion from a mixture of:

Percent Butyl methacrylate S0 Vinylidene chloride 50 The composition is applied both to felt-base wall-covering and flooring material, linoleum, vinyl tile, and asphalt tile. The coating obtained is a clear, stain-resistant Wear layer comparable to that obtained in Example 1.

Example 11 The procedure of Example 2 is repeated with a copolymer prepared in similar fashion from a mixture of:

Percent n-Octyl acrylate 25 Methyl methacrylate 30 Vinylidene chloride 45 The composition is applied both to felt-base Wall-covering and flooring material, linoleum, vinyl tile, and asphalt tile. The coating obtained is a clear, stain-resistant wear layer comparable to that obtained in Example 1.

Example 12 The procedure of Example 2 is repeated with a copolymer prepared in similar fashion from a mixture of:

Percent Lauryl acrylate, 25 Methyl methacrylate 35 Vinylidene chloride 40 The composition is applied both to felt-base wall-covering and flooring material, linoleum, vinyl tile, and asphalt tile. The coating obtained is a clear, stain-resistant wear layer. comparable to that obtained in Example 1.

Example 13 The procedure of Example 2 is repeated with a copolymer prepared in similar fashion from a mixture of:

Percent Lauryl methacrylate 2.5 Methyl methacrylate 25. Vinylidene chloride 50- The composition is applied both to felt-base wall-covering and flooring material, linoleum, vinyl tile, and asphalt tile. The coating obtained is a clear, stain-resistant wear layer comparable to that obtained in Example 1.

Example 1 4 The procedure of Example 2 is repeated with a copolymer prepared in similar fashion from a mixture of:

Percent Stearyl methacrylate 25 Methyl methacrylate 30 Vinylidene chloride 45 The composition is applied both to felt-base wall-covering and flooring material, linoleum, vinyl tile, and asphalt tile. The coating obtained is a clear, stain-resistant wear l-ayer comparable to that obtained in Example 1.

Example 1 5 The procedure of Example 2 is repeated with a copolymer prepared in similar fashion from a mixture of:

7 Percent Stearyl acrylate 25 Vinyltoluene 35 40 Percent Z-ethylhexyl acrylate 15 Methyl, methacrylate 45 Percent 2-et'hylhexyl acrylate 40 Methyl methacrylate 20 Vinylidene chloride 40 (c) Fifty parts by Weight of emulsion from (a) and 50 parts by weight of emulsion from (b) are blended together and the resulting blend is then substituted for the parts of emulsion in parts (b) and (c) in Example 1. Similar results are obtained with the blend as with the emulsion in Example 1.

Example 17 An emulsion copolymer is prepared from a mixture of 20% of ethyl acrylate, 45% of methyl methacrylate, and 35% of vinylidene chloride. A second emulsion copolymer is prepared from a mixture of 30% of ethyl acrylate, 20% of methyl methacrylate, and 50% ofvinylidene chloride; Each of these tWo latices is adjusted to 44% solids concentrations and the pH in each case is adjusted to 8.0, using 14% aqueous ammonium hydroxide. The two polymer dispersions are mixed in 50:50 weight ratio to form a blend of the polymers therein. Then Example 1 is repeated, substituting 100 parts of the resulting blended copolymer dispersion for the emulsion polymer dispersion used in Example 1(b) and (c). The results obtained are quite similar to those obtained in Example 1.

Example 18 (a) An emulsion copolymer is prepared with the following composition, employing 6% t-octylphenoxypolyethoxyethanol containing about 40 oxyethylene units (base on the total weight of the monomers) as the emulsifier and conventional emulsion polymerization The final total solids concentration of the emulsionv is.

(b) There are mixed on a high speed electric stirrer parts of titanium dioxide, 2 parts of formaldehydecondensed sodium naphthalene sulfonate, 38 parts of water and 220 parts of the emulsion from part (a).

(c) Four coats of the resulting coating. composition are applied to unbleached cheesecloth and the finished product is baked for five minutes at 200 F. The product is adhered to a kitchen wall with the coated side exposed. The coating has excellent resistance to staining by iodine, excellent resistance to rub-oil on handling, and shows excellent resistance to wear.

We claim:

1. As an article of manufacture, a flooring material carrying a clear topcoating thereon comprising a copolymer of 35 to 65% by Weight of vinylidene chloride and 35 to 65 by weight of methyl acrylate.

2. As an article of manufacture, a flooring material carrying a clear topcoating thereon comprising a copolymer of 35 to 65 by Weight of vinylidene chloride and 35 to 65% by weight of butyl methacrylate.

3. As an article of manufacture, a flooring material carrying a clear, wear-resistant topcoating thereon comprising a water-insoluble copolymer of 35 to 65% by weight of vinylidene chloride, 10 to 45% by Weight of methyl methacrylate, and 20 to 55% by Weight of at least one ester of acrylic acid with a saturated aliphatic alcohol having 1 to 18 carbon atoms.

4. As an article of manufacture, a flooring material carrying a clear, wear-resistant topcoating thereon comprising a water-insoluble copolymer of 35 to 65% by weight of vinylidene chloride, to 45% by Weight of styrene, and to 55% by Weight of at least one ester of acrylic acid with a saturated aliphatic alcohol having 1 to 18 carbon atoms.

5. As an article of manufacture, a flooring material carrying a clear, Wear-resistant topcoating thereon comprising a Water-insoluble copolymer of 35 to 65% by weight of vinylidene chloride, 10 to 45% by weight of vinyltoluene, and 20 to 55% by Weight of at least one ester of acrylic acid with a saturated aliphatic alcohol having 1 to 18 carbon atoms.

6. As an article of manufacture, a flooring material carrying a clear, wear-resistant topcoating thereon comprising a water-insoluble copolymer of 35 to 65% by weight of vinylidene chloride, 10 to 45% by weight of methyl methacrylate, and 20 to 55% by weight of at least one ester of methacrylic acid with a saturated aliphatic alcohol having 3 to 18 carbon atoms.

7. As an article of manufacture, a flooring material carrying a clear, wear-resistant topcoating thereon comprising a water-insoluble copolymer of 35 to 65% by weight of vinylidene chloride, 10 to 45% by weight of methyl methacrylate, and 20 to 55 by weight of butyl methacrylate.

8. As an article of manufacture, a flooring material carrying on the wear surface thereof a clear topcoating comprising a copolymer of about 40% by weight of vinylidene chloride, about by weight of 2-ethylhexyl acrylate, and about by Weight of methyl methacrylate.

9. As an article of manufacture, a flooring material carrying on the wear surface thereof a clear topcoating comprising a copolymer of about by weight of vinylidene chloride, about 20% of methyl methacrylate, and about 40% of ethyl acrylate.

10. As an article of manufacture, a flooring material carrying on the wear surface thereof a clear topcoating comprising a copolymer of about 40% by weight of vinylidene chloride, about 7% of methyl methacrylate, about 3% by Weight of methacrylic acid, and about of ethyl acrylate.

11. As an article of manufacture, a solid material adapted for use in the surfacing of walls and floors, said material carrying a wear-resistant topcoating thereon comprising a water-insoluble emulsion copolymer of a mixture of (A) 35 to 65% by weight of vinylidene chloride with (B) 65 to 35% by weight respectively of a monomeric material selected from the group consisting of (a) methyl acrylate, (b) n-propyl methacrylate, (c) butyl methacrylate, and (d) mixtures of (1) at least one member having a hardening effect, in an amount of 10 to 50% by weight based on the total monomer weight, selected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effect, in an amount of 15 to by weight based on the total monomer weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least 35% by weight of the copolymer is formed of at least one of the aforesaid esters mentioned in (l) and (2).

12. As an article of manufacture, a felt base material carrying on the exposed surface thereof a clear topcoating comprising a water-insoluble emulsion copolymer of a mixture of (A) 35 to 65% by weight of vinylidene chloride with (B) 65 to 35 by weight respectively of a monomeric material selected from the group consisting of (a) methyl acrylate, (b) n-propyl methacrylate, (c) butyl methacrylate, and (d) mixtures of (l) at least one member, in an amount of 10 to 50% by weight based on the total monomer weight, having a hardening effect selected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effect, in an amount of 15 to 5 5% by weight based on the total monomer Weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least 35% by eight of the copolymer is formed of at least one of the aforesaid esters mentioned in (1) and (2).

13. As an article of manufacture, a linoleum carrying on the exposed surface thereof a clear topcoating comprising a water-insoluble emulsion copolymer of a mixture of (A) 35 to 65 by weight of vinylidene chloride with (B) 65 to 35 by weight respectively of a monomeric material selected from the group consisting of (a) methyl acrylate, (b) n-propyl methacrylate, (c) butyl methacrylate, and (d) mixtures of (1) at least one member having a hardening efiect, in an amount of 10 to 50% by weight based on the total monomer weight, selected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effect, in an amount of 15 to 55% by weight based on the total monomer Weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least 35% by weight of the copolymer is formed of at least one of the aforesaid esters mentioned in (1) and (2).

14. As an article of manufacture, an asphalt tile carrying on the exposed surface thereof a clear topcoating comprising a water-insoluble emulsion copolymer of a mixture of (A) 35 to 65 by weight of vinylidene chloride with (B) 65 to 35 by weight respectively of a monomeric material selected from the group consisting of (a) methyl acrylate,

(b) n-propyl methacrylate,

(c) butyl methacrylate, and

(:1) mixtures of (1) at least one member having a hardening effect, in an amount of 10 to 50% by weight based on the total monomer weight, se-

1 1 lected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effect, in an amount of 15 to 55 by weight based on the total monomer weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least 35% by Weight of the copolymer is formed of at least one of the aforesaid esters mentioned in (l) and (2).

15. As an article of manufacture, a vinyl tile carrying on the exposed surface thereof a clear topcoating comprising a water-insoluble emulsion copolymer of a mixture of (A) 35 to 65% by weight of vinylidene chloride with (B) 65 to 35% by weight respectively of a monomeric material selected from the group consisting of (a) methyl acrylate, (b) n-propyl methacrylate, (c) butyl methacrylate, and (d) mixtures of (l) at least one member having a hardening effect, in an amount of to 50% by weight based on the total monomer weight, selected from the group consisting of sty rene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effect, in an amount of to 55% by weight based on the total monomer weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least 35% by weight of the copolymer is formed of at least one of the aforesaid esters mentioned in (1) and (2).

16. As an article of manufacture, a wall-covering material carrying on the exposed surface thereof a clear topcoating comprising a water-insoluble emulsion copolymer of a mixture of (A) 35 to 65% by Weight of vinylidene chloride with (B) 65 to 35 by weight respectively of a monomeric material selected from the group consisting of (a) methyl acrylate, (b) n-propyl methacrylate, (c) butyl methacrylate, and (d) mixtures of (1) at least one member having a hardening effect, in an amount of 10 to 50% by weight based on the total monomer weight, selected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effect, in an amount of 15 to 55% by Weight based on the total monomer Weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having fiom 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least 35% by (B) 65 to 35 by weight respectively of polymerized monomeric material selected from the group consisting of (a) methyl acrylate,

(b) n-propyl methacrylate,

(c) butyl methacrylate, and

(d) mixtures of (1) at least one member having a hardening,

effect, in an amount of 10 to 50% by weight based on the total monomer weight, selected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effect, in an amount of 15 to 55% by weight based on the total monomer weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least, 35% by weight of the copolymer is formed of at least one of the aforesaid esters.

18. As an article of manufacture, a solid material carrying on the exposed surface thereof a topcoating comprising a blend of at least two water-insoluble emulsion copolymers containing 35 to 65% by weight of vinylidene, chloride, the average composition of the blend being (A) 35 to 65 by weight of polymerized vinylidene chloride and (B) 65 to 35% by weight respectively of a polymerized monomeric material consisting of mixtures of (l) at least one member having a hardening effect, in an amount of 10 to 50% by weight based on the total monomer weight, selected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effeet, in an amount of 15 to 55% by weight based on the total monomer weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least 35 by weight of the copolymer is formed of at least one of the foresaid esters mentioned in (l) and (2), at least one of the copolymers being a copolymer of 35-65% by weight of vinylidene chloride,

3565% by weight of at least one hardening comonomer of (1) above, and

0 to 20% by weight of at least one softening comonomer of (2) above, and at least one other copolymer of the blend being a copolymer of 35 to 65 by weight of vinylidene chloride,

10 to 30% by weight of at least one hardening comonomer of (1) above, and

20 to 55 by weight of at least one softening comonomer of (2) above.

13 19. As a composition of matter, a blend of at least two water-insoluble emulsion copolymer containing 35 to 65% by weight of vinylidene chloride, the average composition of the blend being (A) 35 to 65% by weight of polymerized vinylidene chloride and (B) 65 to 35% by weight respectively of polymerized monomeric material selected from the group consisting of (a) methyl acrylate, (b) n-propyl methacrylate, (c) butyl methacrylate, and (d) mixtures of (1) at least one member having a hardening effect, in an amount of to 50% by weight based on the total monomer weight, selected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effect, in an amount of to 55% by weight based on the total monomer weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least 35% by weight of the copolymer is formed of at least one of the aforesaid esters. 20. As a composition of matter, a blend of at least two water-insoluble emulsion copolymers containing 35 to 65% by weight of vinylidene chloride, the average composition of the blend being (A) 35 to 65% by wei ht of polymerized vinylidene chloride and 14 (B) 65 to by weight respectively of a polymerized monomeric material consisting of mixtures of (1) at least one member having a hardening effeet, in an amount of 10 to by weight based on the total monomer weight, selected from the group consisting of styrene, vinyltoluene, and esters of methacrylic acid with an alkanol having 1 to 3 carbon atoms, with (2) at least one member having a softening effect, in an amount of 15 to by weight based on the total monomer weight, selected from the group consisting of esters of acrylic acid with a saturated aliphatic alcohol having from 1 to 18 carbon atoms and esters of methacrylic acid with a saturated aliphatic alcohol having from 4 to 18 carbon atoms,

with the proviso that at least 35% by weight of the copolymer is formed of at least one of the aforesaid esters mentioned in and at least one of the copolymers being a copolymer of 35-65% by weight of vinylidene chloride, 35-65% by weight of at least one hardening comonorner of (1) above, and 0 to 29% by weight of at least one softening comonomer of (2) above, and at least one other copolymer of the blend being a copolymer of 35 to by weight of vinylidene chloride, 10 to 30% by weight of at least one hardening comonomer of (1) above, and 2-0 to 55 by weight of at least one softening comonomer of (2) above.

References Cited in the file of this patent UNITED STATES PATENTS 2,707,157 Stanton et al. Apr. 26, 1955 2,769,726 Wetterau et al. Nov. 6, 1956 2,774,685 Carnegie Dec. 18, 1956 

1. AS AN ARTICLE OF MANUFACTURE, A FLOORING MATERIAL CARRYING A CLEAR TOPCOATING THEREON COMPRISING A COPOLYMER OF 35 TO 65% BY WEIGHT OF VINYLIDENE CHLORIDE AND 35 TO 65% BY WEIGH TO FMETHYL ACRYLATE. 